Acenaphthotriazole and Its Kuratowski Complex: A π‐Extended Tecton for Supramolecular and Coordinative Self‐Assembly

• Published in: Chemistry : a European journal Vol. 28; no. 4
• Main Authors: Knippen, Katharina, Matuszczyk, Daniel, Kraft, Maryana, Bredenkötter, Björn, Eickerling, Georg, Lis, Tadeusz, Volkmer, Dirk, Stępień, Marcin
• Format: Journal Article
• Language: English
• Published: Weinheim Wiley Subscription Services, Inc 01.01.2022
• Subjects: Assembly; Chemistry; Computer applications; Crystal structure; Crystals; Fluorescence; Magnetic resonance spectroscopy; Molecular structure; NMR; NMR spectroscopy; Nuclear magnetic resonance; Triazoles
• ISSN: 0947-6539; 1521-3765
• DOI: 10.1002/chem.202103480

π‐Extended acenaphtho[1,2‐d][1,2,3]triazoles, the unsubstituted Anta‐H and its di‐tert‐butyl derivative Dibanta‐H, as well as 5,6,7,8‐tetrahydro‐1H‐naphtho[2,3‐d][1,2,3]triazole Cybta‐H were obtained in concise syntheses. In the solid state, Dibanta‐H forms an unprecedented hydrogen‐bonded cyclic tetrad, stabilized by dispersion interactions of the bulky tBu substituents, whereas a cyclic triad was found in the crystal structure of Anta‐H. These cyclic assemblies form infinite slipped stacks in the crystals. Evidence for analogous hydrogen‐bonded self‐assembly in solution was provided by low‐temperature NMR spectroscopy and computational analyses. Kuratowski‐type pentanuclear complexes [Zn5Cl4(Dibanta)6] and [Zn5Cl4(Cybta)6] were prepared from the respective triazoles. In the Dibanta complexes, the π‐aromatic surfaces of the ligands extend from the edges of the tetrahedral Zn5 core, yielding an enlarged structure with significant internal molecular free volume and red‐shifted fluorescence.